Polymeric support

Polymerization. Supported catalysts are used extensively in olefin polymerization, primarily to manufacture polyethylene and polypropylene. Because propylene can polymerize in a stereoregular manner to produce an isotactic, or crystalline, polymer as well as an atactic, or amorphous, polymer and ethylene caimot, there are large differences in the catalysts used to manufacture polyethylene and polypropylene (see Olefin polymers). 

In addition to polymeric support media, capillaries and flowing buffers have been used as support media for electrophoresis. Although these are not used as frequendy, there are definite advantages for certain types of samples and appHcations. 

J.W. Labadie, Polymeric Supports for Solid Phase Synthesis, Curr Opin Chem Biol 2 346-352 1998. 

Beaded polymeric support, whether polystyrene-divinylbenzene, polymethacrylate, or polyvinyl alcohol, is conventionally produced by different variations of a two-phase suspension polymerization process, in which liquid microdroplets are converted to the corresponding solid microbeads (1). 

Beaded polymeric supports are produced by a two-phase suspension polymerization in which microdrops of a monomer solution are directly converted to the corresponding microbeads. The size of a microdroplet is usually determined by a number of interrelated manufacturing parameters, which include the reactor design, the rate of stirring, the ratio of the monomer phase to water, the viscosity of both phases, and the type and concentration of the droplet stabilizer. 

The pore size, the pore-size distribution, and the surface area of organic polymeric supports can be controlled easily during production by precipitation processes that take place during the conversion of liquid microdroplets to solid microbeads. For example, polystyrene beads produced without cross-linked agents or diluent are nonporous or contain very small pores. However, by using bigb divinylbenzene (DVB) concentrations and monomer diluents, polymer beads with wide porosities and pore sizes can be produced, depending on the proportion of DVB and monomer diluent. Control of porosity by means of monomer diluent has been extensively studied for polystyrene (3-6) and polymethacrylate (7-10). 

Synthetic organic polymers, which are used as polymeric supports for chromatography, as catalysts, as solid-phase supports for peptide and oligonucleotide synthesis, and for diagnosis, are based mainly on polystyrene, polystyrene-divinylbenzene, polyacrylamide, polymethacrylates, and polyvinyl alcohols. A conventional suspension of polymerization is usually used to produce these organic polymeric supports, especially in large-scale industrial production. 

New templated polymer support materials have been developed for use as re versed-phase packing materials. Pore size and particle size have not usually been precisely controlled by conventional suspension polymerization. A templated polymerization is used to obtain controllable pore size and particle-size distribution. In this technique, hydrophilic monomers and divinylbenzene are formulated and filled into pores in templated silica material, at room temperature. After polymerization, the templated silica material is removed by base hydrolysis. The surface of the polymer may be modified in various ways to obtain the desired functionality. The particles are useful in chromatography, adsorption, and ion exchange and as polymeric supports of catalysts (39,40). 

High-performance size exclusion chromatography is used for the characterization of copolymers, as well as for biopolymers (3). The packings for analyses of water-soluble polymers mainly consist of 5- to 10-/Am particles derived from deactivated silica or hydrophilic polymeric supports. For the investigation of organosoluble polymers, cross-linked polystyrene beads are still the column packing of choice. 

The use of a polymeric support also affords a unique opportunity to control independently the variables that may affect the chiral recognition process, which is hard to achieve with silica. For example, the type and number of reactive sites can be easily adjusted with a polymer support. We recently reported an extensive study of the... 

Peptide synthesis requires the use of selective protecting groups. An N-protected amino acid with a free carboxyl group is coupled to an O-protected amino acid with a free amino group in the presence of dicydohexvlcarbodi-imide (DCC). Amide formation occurs, the protecting groups are removed, and the sequence is repeated. Amines are usually protected as their teit-butoxy-carbonyl (Boc) derivatives, and acids are protected as esters. This synthetic sequence is often carried out by the Merrifield solid-phase method, in which the peptide is esterified to an insoluble polymeric support. 

The different interactions of the microwave radiation with the solvent and with the polymeric support might also cause interesting effects. Many authors... 

Soluble polymers have also been used as support. These exploit the combined advantage of homogeneous with those of soHd-phase chemistry [36]. PEG linked 5-bromothiophene-2-carboxyUc acid was cross-coupled with several arylboronic acids under microwave irradiation (constant power of 75 W) using water as the solvent (Scheme 17). Interestingly, microwave irradiation gave less ester cleavage than classical heating (70 °C). The polymeric support remained stable under both conditions. 

A catalyst molecule bound to a polymeric support may be less active than in homogeneous solution, or exhibit different reactivity... 

Gulea M, Masson S (2003) Recent Advances in the Chemistry of Difunctionalized Organo-Phosphorus and -Sulfur Compounds. 229 161-198 Haag R, Roller S (2004) Polymeric Supports for the Immobilisation of Catalysts. 242 1-42 Hackmann-Schlichter N,see Krause W (2000) 210 261-308 Hadjiaraoglou LP, see de Meijere A (2000) 207 149-227... 

In the Fmoc protection approach, the acid-labile ferf-butyl groups are often used for side-chain protection. The base-labile Fmoc groups can be easily removed during a synthesis using piperidine (Fig. 4). The final global deprotection together with cleavage from the polymeric support is achieved with TFA. 

There is a whole spectrum of heterogeneous catalysts, but the most common types consist of an inorganic or polymeric support, which may be inert or have acid or basic functionality, together with a bound metal, often Pd, Pt, Ni or Co. Even if the support is inert its structure is of vital importance to the efficiency of the catal ic reaction. Since the reactants are in a different phase to the catalyst both diffusion and adsorption influence the overall rate, these factors to some extent depending on the nature and structure of the support. 

In the first place the ease of these reactions depends on the swelling behavior of the polymeric support. If the liquid employed for dissolving the metal precursor swells the support to a relatively high extent, the interior of the swollen polymer will be readily accessible (Figure 7) [30]. 

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